Synthesen und Kristallstrukturuntersuchungen von Pentacarbonylwolfram-Komplexen mit Tetra-tert.-butylcyclotetrastiban und Tetraphenyldistiban als Liganden

Syntheses and Crystal Structure Analyses of Pentacarbonyl Tungsten Complexes with Tetratert.butyl Cyclotetrastibane and Tetraphenyldistibane Ligands The synthesis of (tBuSb)₄[W(CO)₅]₂ ( 1 ) is performed by reaction of (tBuSb)₄ with W(CO)₅THF in a 1:2 molar ratio. The reaction in the 1:1 ratio gives (tBuSb)₄W(CO)₅ ( 2 ). The crystal structures of 1 and (Ph₄Sb₂)[W(CO)₅]₂ ( 3 ) are reported.     

Darstellung und spektroskopische Charakterisierung von Fluortrichlor-arsoniumhexafluoroarsenat,AsFCl3+AsF6−

Preparation and Spectroscopic Characterization of Fluorotrichloroarsonium Hexafluoroarsenate, AsFCl₃⁺AsF₆^? The mixed halide pniktide cation AsFCl₃⁺ is prepared by oxidative fluorination of AsCl₃ with XeF⁺ AsF₆^?. AsFCl₃⁺ AsF₆^? is characterized by IR, Raman, and ¹⁹F-NMR spectroscopy.     

Darstellung und Kristallstruktur von PI4+ AlI4−

Preparation and Crystal Structure of PI₄⁺AlI₄^? PI₄⁺AlI₄^? was prepared and its crystal structure determined by single crystal X-ray data (orthorhombic, Pna2₁, a = 1109.4, b = 1048.5, c = 1529.3 pm, V = 1778.8 · 10⁶ pm³, Z = 4). The nearly tetrahedral cations and anions (mean P? I and Al? I distances: 239.6 and 251.8 pm respectively) are connected to a three-dimensional structure by weak iodine-iodine bonds (338.6–345.1 pm).     

Darstellung und Charakterisierung von Thiocyanatderivaten der Hydroboratanionen B10H102− und B12H122−

Preparation and Characterization of Thiocyanate Derivatives of the Hydroborate Anions B₁₀H₁₀^2? and B₁₂H₁₂^2? The reaction of B₁₀H₁₀^2? or B₁₂H₁₂^2? with (SCN)₂ in dichloromethane yields mixtures of thiocyanatohydroborates from which the pure isomers 1-and 2-(SCN)B₁₀H₉^2?, 1, 10-(SCN)₂B₁₀H₈^2?, and 1-(SCN)B₁₂H₁₁^2? are isolated by ion exchange chromatography on diethylaminoethyl cellulose. The structures are determined by ¹¹B and ¹¹B{¹H}NMR spectroscopy. There are characteristic chemical shifts due to apical and equatorial substituents, respectively. In B₁₀H₁₀^2? the substitution at apical positions is prefered. The IR and Raman spectra are similar to those of isosteric halogeno derivatives in the region of ν(BH) and of the borate cages. Because of the high frequencies of ν(CN): 2120–2140 cm^?1 S coordination of SCN^? is supposed.     

Darstellung von Austauschern mit Kryptanden als Ankergruppen

Ohne Zusammenfassung     

Eisen- und Mangankomplexe mit sauerstoff-, schwefel- und methylen-verbrückten Distibanen und mit Chlorodiphenylstiban als Liganden

Complexes of Iron and Manganese with Oxygen-, Sulfur-, and Methylene-bridged Distibines and with Chlorodiphenylstibine as Ligands The photochemical reaction of CO₃Fe[P(OPh)₃]₂ and of MeCpMn(CO)₃ with the stibines Ph₂SbCl and (Ph₂Sb)₂X (X = O, S and CH₂) yields mononuclear complexes (CO)₂[P(OPh)₃]₂FeL and °Cp(CO)₂MnL (L = Ph₂SbCl, (Ph₂Sb)₂X) and the stibine bridged binuclear complexes °CO)₂[P(OPh)₃]₂Fe{(Ph₂Sb)₂X}Fe(CO)₂[P(OPh)₃]₂ and °Cp(CO)₂Mn{(Ph₂Sb)₂X}Mn(CO)₂MeCp.     

Synthesen und Kristallstrukturen von Cu‐ und Ag‐Komplexen mit [Ta6S17]4—‐Ionen als Liganden

Syntheses and Crystal Structures of Cu and Ag Complexes with [Ta₆S₁₇]^4— Ions as Ligands In the presence of phosphines saturated solutions of the thiotantalates (NEt₄)₄[(Ta₆S₁₇)] · 3MeCN react with copper or silver salts to give new heterobimetallic Ta—M—S clusters (M = Ag, Cu). These clusters contain the intact cluster core of the [Ta₆S₁₇]^4— anion. Compounds [Cu(PMe₃)₄]₃[(Ta₆S₁₇)Cu(PMe₃)] · 2MeCN ( 1 ), (NEt₄)[(Ta₆S₁₇)Ag₃(PMe₂ⁱPr)₆] · 5MeCN ( 2 ), [(Ta₆S₁₇)Cu₄ (PMe₂ⁱPr)₈] · MeCN ( 3 ), [(Ta₆S₁₇)Cu₅Cl(PMe₂ⁱPr)₉] · MeCN ( 4 ) and [Ta₂Cu₂S₄Cl₂(PMe₂ⁱPr)₆] · 2MeCN ( 5 ) are presented herein. The structures of these compounds were elucidated by single crystal X‐ray structural analyses.     

Darstellung und Kristallstruktur eines Calciumcarbidchlorides mit einer C34−-Einheit,Ca3Cl2C3

Synthesis and Crystal Structure of a Calciumcarbide Chloride Containing a C₃^4? Unit, Ca₃Cl₂C₃ Ca₃Cl₂C₃ was prepared from calcium, CaCl₂ and graphite in sealed tantalum capsules. Red, transparent crystals were obtained from heating the mixture to 900°C (for one day) and annealing afterwards at 780°C for three days. The compound forms a layered structure (Cmcm, Z = 4, a = 384.24(9) pm, b = 1340.7(3) pm, c = 1152.6(3) pm, R = R_W = 0.036 for 481 independent intensities) with alternating stacks of double layers of Ca²⁺ and monolayers of Cl^?. The double layers of calcium contain allylenide ions, C₃^4?. The latter exhibit C_2v symmetry, a bond angle (C? C? C) of 169.0(6)° and a C? C separation of 134.6(4) pm.     

Konfiguration und konformation von methyl- und aminylradikalen mit CF3S-substituenten

From the hyperfine ESR-splitting patterns of, $\text{a(}{}^{13}\text{C}{}_{\mathrm{\gamma }}\text{), a(}{}^{14}\text{N}\text{)}\text{and}\text{a(}{}^{19}\text{F}\text{)}$ it is concluded that the radicals (CF₃S)₃C·, (CF₃S)₂HC·, (CF₃S)H₂C·, (CF₃S)₂N· and (CF₃S)₃Si· are planar π-radicals existing in a nearly fully staggered conformation. The force which promotes the staggered conformation arises from conjugative delocalization between the 2 p_z-unpaired electron and the p-type lone pair on the sulfur atoms of the CF₃S-groups, causing a stabilization of the radicals. The electronegative CF₃-group decreases the extent of conjugative electron delocalization.Whereas fluorine atoms adopt equivalent positions in the radicals the staggered conformation implies inequivalence of the protons in CF₃SCH₂.     

Bildung,Kristallstruktur und absolute Konfiguration von (−)-N-(Chloromethyl)galanthaminium-chlorid

Formation, X-Ray Crystal Structure, and Absolute Configuration of (?)-N-(Chloromethyl)galanthaminium Chloride The acetylcholinesterase inhibitor galanthamine ( 1 ), main alkaloid of several Narcissus species, readily forms a quaternary ammonium salt by reaction with the solvent CH₂Cl₂. The structure and absolute configuration of (?)-N-(chloromethyl)galanthaminium chloride ( 2 ) were determined by X-ray diffraction (R = 0.075 for 2775 observed independent reflexions) and NMR spectroscopy. The tetragonal crystals (space group P4₃) contain two crystallographically independent cations which do not differ significantly from one another. The CH₂Cl group is attached to the quaternary N-atom in stereospecific (R)-configuration. In the crystal, the configurational position of the Me group at the N-atom of 2 differs from that of the crystalline free base 1 . Hydrogen bonding is observed from the OH group at C(3) of 2 to the Cl^? anion or to the Cl-atom of an adjacent cation.     

Darstellung und Strukturen von Mg‐Komplexen mit α, ω‐Dicarboxylato‐Liganden (Dicarboxylat = Succinat,Glutarat und Suberat)

Syntheses and Structures of Magnesium Complexes with α, ω‐Dicarboxylato Ligands; Dicarboxylate = Succinate, Glutarate, and Suberate Crystals of (Tetraaqua)(succinato)magnesium ( 1 ), (Tetraaqua)(glutarato)magnesium ( 2 ) und (Triaqua)(suberato)magnesium ( 3 ) were obtained by layering an aqueous solution of the respective sodium salt with a solution of MgCl₂ in isopropanol. In 1 a chain structure is realized. Mg(H₂O)₄ units are bridged in trans orientation by α, ω‐bonded succinate groups. 2 contains also chains. Glutarato groups are bonded in a cis fashion to Mg(H₂O)₄ units. They form bridges by using their two α O atoms. 3 represents a layer structure. The basic structural motives are α, α, ω‐bonded suberate, and fac‐Mg(H₂O)₃ units. All three structures contain efficient H bridging systems. The connection between the symmetry of the polymeric groups (chains or layer) and the symmetry of the underlying space groups is discussed. 1 : Space group P2₁/c, Z = 4, lattice constants at 20 °C: a = 7.441(2), b = 14.827(2), c = 7.771(2) Å; β = 99.77(3)°, R1 = 0.052. 2 : Space group C2/c, Z = 8, lattice constants at 20 °C: a = 12.867(2), b = 7.109(1), c = 21.683(3) Å; β = 107.33(2)°; R₁ = 0.032. 3 : Space group P2₁/a, Z = 4, lattice constants at 20 °C: a = 9.174(2), b = 8.071(2), c = 15.960(3) Å; β = 104.29(2)°; R₁ = 0.052.     

Darstellung von CF3SClF+MF6− (M = As,Sb) und Kristallstruktur von CF3SCl2+SbF6−

Preparation of CF₃SClF⁺MF₆^? (M = As, Sb) and Crystal Structure of CF₃SCl₂⁺SbF₆^? CF₃SClF⁺MF₆^? (M = As, Sb) is prepared by oxidative fluorination of CF₃SCl with XeF⁺MF₆^?. The new salt is characterized by IR, Raman and NMR spectra in comparison with CF₃SF₂⁺MF₆^? and CF₃SCl₂⁺MF₆^?. In SO₂ solution CF₃SClF⁺SbF₆^? symmetrizises into CF₃SF₂⁺SbF₆^? and crystalline CF₃SCl₂⁺SbF₆^? with the monoclinic space group P2₁/c with a = 773.5(14) pm, b = 954.8(15) pm, c = 1242.0(18) pm, β = 100.24(8)°, Z = 4.